Phthalocyanine compounds

ABSTRACT

Watersoluble condensation products of 2 Moles of a compound or two different compounds of the formula WHEREIN PC stands for a metal-free or metal-containing phthalocyanine radical bearing two or three SO3H- and/or A for an organic bridge-member, each of R1 and R2 for hydrogen or lower (substituted) alkyl, each of X and Y for hydrogen or lower (hydroxy) alkyl, with 1 Mol of cyanuric halide, as dyes with good wash-off and build-up properties, especially good for printing and exhaustion dyeing.

I Elmted States Patent [151 3,674,783

Von Tobel July 4, 1972 [54] PHTHALOCYANINE COMPOUNDS Primary Examiner-Henry R. Jiles Assistant Examiner-Harry l. Moatz 7 l 21 Inventor 1223s Von Tobel, Rlehen, Basel, Swltzer Attorney hmepage Quamtance y & Alsenberg [73] Assignee: Sandoz Ltd., Basel, Switzerland [57] ABSTRACT [22] .Filedi Ju 1969 Watersoluble condensation products of 2 Moles of a com- [21 APPL No 833,732 pound or two different compounds of the formula I'M R2 [52] US. Cl ..260/242, 260/146 T, 260/147, (PC)SO NAI I-H 260/153, 260/240 B, 260/2493, 260/3145, 8/1 wherein PC stands for a metal-free or metal-containing 1 Inl. Cl. phthalocyanine radical bea ing two or three and/0| [58] Field of Search .260/242, 314.5,153, 146,147,

[56] References Cited SOa-N\ -groups,

Y UNlTED STATES PATENTS 2,219,330 10/1940 Nadler 260/3145 A for an organic bridge-member, each of R and R for 2,706,199 4/1955 Bremaflo-u hydrogen or lower (substituted) alkyl, each of X and Y for 2,776,957 1/1957 Brenlfino hydrogen or lower (hydroxy) alkyl, with 1 M01 of cyanuric ha- 2 5 8/1966 Heyna 314-5 lide, as dyes with good wash-off and build-up properties, espe- 3,334,1 Bryan 61 good for rinting and exhaustion 3,040,021 6/1962 Gurst ..260/153 11 Claims, No Drawings PHTHALOCYANINE COMPOUNDS This invention relates to phthalocyanine compounds of the formula where (PC) and (PC)' stand for the same or different phthalocyanine radicals, each of which contains 2 or 3 80 and/or /X S 02N\ -groups,

A, stands for a divalent bridge member of the aliphatic, aromatic, aliphatic-aromatic cycloaliphatic or heterocyclic series which may be interrupted by hetero atoms or groups of hetero atoms, A; for a divalent bridge member of the aliphatic, aromatic, aliphatic-aromatic, cycloaliphatic or heterocyclic series which may be interrupted by hetero atoms or groups of hetero atoms, each of the substituents R R R and R stands for hydrogen or a lower alkyl radical which may be substituted, both the substituents X and Y stand for hydrogen or a lower alkyl or hydroxyalkyl radical, and where the dye molecule as a whole bears a number of water-solubilizing groups required to impart solubility in water.

The process for the production of the phthalocyanine compounds of Formula (I), consists in reacting 1 mole of a cyanuric halide in either order with 1 mole of a compound of formula Examples of suitable water-solubilizing groups are sulphonic acid, carboxylic acid, methylsulphonyl and ethylsulphonyl groups and the sulphonamide group, which latter group may be monosubstituted, preferably by lower hydrocarbon radicals. The phthalocyanine compounds of Formula (I) bear at least four or five sulphonic acid groups to render them sufficiently soluble in water for practical application. At the other extreme it is hardly possible to introduce more than 14 sulphonic acid groups into the dye molecule. It is preferable for the phthalocyanine compounds of Formula (I) to contain six to 12 sulphonic acid groups, some of which may be replaced by carboxylic acid, alkylsulphonyl or optionally monosubstituted sulphonamide groups. lt is to be noted, however, that the water-solubilizing action of the carboxylic acid group and the optionally monosubstituted sulphonamide group is heavily pH-dependent. In the cold only the salts of the alkali metals of these groups have effective solubilizing action; the acid forms are considerably less effective.

Other groups exercising slight to very slight water-solubilizing action, such as hydroxyl, acetylamino, carbomethoxyamino, carbethoxyamino and disubstituted sulphonamide groups, are of only minor importance.

The most suitable cyanuric halides are cyanuric bromide and cyanuric chloride, of which the latter is preferred.

The compound of Formula ([1) can be prepared by reacting a chloride of phthalocyanine triand/or tetra-sulphonie acid with a compound of the formula where Z represents a nitro group,

a group or a group Ilia 1?: NH Nacyl:

or of the group by saponification into Llu' group The compound of Formula (lll) can be produced in an analogous manner.

The hthalocyanine triand/or tetra-sulphonic acid chlorides are derived from metal-free phthalocyanine or from metal-containing phthalocyanines, preferably nickel or copper phthalocyanines. They bear the sulphonic acid chloride groups in the 3-positions of the benzene nuclei if they are produced by direct sulphochlorination, or in the 4positions if they are obtained from the analogous sulphonic acids.

The substituents R R R and R represent preferably, hydrogen atoms, lower (i.e. with one to about five carbon atoms) alkyl, hydroxyalkyl, alkoxyalkyl or halogenoalkyl radicals, or benzyl radicals. If the radical A or A is aromatic or cycloaliphatic, it is advisable to choose hydrogen atoms or aliphatic radicals as R,, R R or R The bridge member A, m A; may bl an aliphatic radlcal, such as an urmuatic radical, such as ail a cycloaliphatic radical, such as or an aliphatic-aromatic radical, such as and 5 ,x soar sour The acyl substitutent in the radical I --Nacyl SOQH .l 50311 is preferably acetyl, propionyl, methoxycarbonyl or ethox- It; may be interrupted by hetero atoms or groups of ycarbonyl'The radlcal hetero atoms, e.g. X

--N -oHr-oH2-0 cm- HF. -CHQCH2 -C \Y w is preferably the amino group or a methylamino, O- 7' dimethylamino, ethylamino, diethylamino, 2-hydroxyethylamino, di-(Z-hydroxyethyl)-amino, 2- or 3- hydrox ypropylamino or 3-hydroxybutylamino group.

Very good properties are shown by phthalocyanine dyes of 0st: .O thefonnula -Nw where P and PC' stand for the radicals of copperor 40 nickel-containing phthalocyanines; X X Y and Y inde- Hosb 303B pendently of each other, for hydrogen or lower alkyl or hydroxyalkyl radicals; Hal for bromine or preferably chlorine; and m, n, p and r for whole numbers from 1 to 3, where n m -C -N=N p r= 4; in particular dyes in which at least one of the radicals PC" and PC' stands for a nickel-containing phthalocyanine radical and at least one of the bridge members A and 3 A bears an azo group. H0 S The cyanuric halide can be conveniently reacted with a compound of Formula (II) or (III) in aqueous medium at 5 N TN I to 20C, or preferably at 0-5C, and at a weakly acid to neutral reaction, e.g., in the pH region of 3 to 7 or preferably, CH3 4 to 6. The cyanuric halide is employed as it is or in solution in H 0 an organic solvent, such as acetone.

- N For the second reaction it is best to apply temperatures of C V \77 30 to 70C or preferably, 4050C and to work in the pH region of 5 to 9 or preferably, 6 to 8.

The phthalocyanine compounds of Formula (I) thus formed can be precipitated by the addition of salt, filtered ofl with Q suction, washed and dried. Depending on the compounds C selected for the reaction, reactive dyes for cellulosic fibers are obtained having certain specific properties. Thus, when A, and/or A are small radicals, such as alkylene or phenylene radicals, and the number of sulphonic acid groups is limited,

H0 for example, to six, dyes with good power of build-up suitable ,OAJHZCH for exhaustion dyeing are obtained, whilst a greater number of such groups, for example eight, results in dyes of lower sub- S 5 SIEISH stantlvity which hence are easier to wash off and are specially CH3 suitable for printing. Components in which the sulphonic acid groups are in the 4-position of the phthalocyanine molecule give less substantive dyes than those bearing the SO;,H

N groups in the 3-position.

2 The properties of the dyes of Formula (I) are above the ex- N=N pected average of the corresponding dyes, which contain only one phthalocyanine radical.

For example, the dye of the formula (SOgH)3 (S BH)3 NIL N I =1 The good properties shown by the dyes of this invention are surprising, since with reactive dyes an enlargement of the molecule generally has an adverse effect.

The new phthalocyanine compounds of Formula (I) which contain as A and/or A small radicals such as alkylene or phenylene radicals and eight or more water-solubilizing groups, preferably sulphonic acid and/or optionally substituted sulphonamide groups, have good solubility in water, good stability in printing pastes and padding liquors, good compatibility with salts and hard water, good reactivity with cotton, linen and other naturalcellulosic fibers, and with regenerated cellulosic fibers such as viscose filament yarn,

viscose staple fibers and cuprammonium rayon.

Phthalocyanine compounds of Formula (1) containing as A and/or A larger radicals with substantive properties, e.g.,

H 0 3 L I ""N bOzH SOaH U H3 are suitable for exhaustion dyeing even if they contain eight or more, e.g., up to 12, water-solubilizing groups. These dyes are unaffected by the ions of heavy metals, such as copper, iron and chromium ions, and they reserve acetate, triacetate, polyester, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate and polyalkylene fibers. As their substantivity is only moderate, the unfixed proportion of dye can be washed off with ease.

The copper-containing dyes of Formula (I) in which the bridge members A, and A, stand for optionally substituted aliphatic and/or phenylene radicals have a pleasing turquoiseblue shade. If the compounds of Formulae (11) and (111) are chosen so that at least one of the bridge members A and A contains an azo group and at least one of the radicals (PC) and (PC) stands for a nickelcontaining phthalocyanine radical, attractive green dyes are obtained which are notable for their good light fastness in dyeings on cellulosic fibers.

Goods of cellulosic fiber dyed, padded or printed with the dyes of this invention are aftertreated in alkaline medium, if necessary at high temperature, and then soaped, rinsed and dried. The dyeings have good fastness to light in the dry and wet states and to wet treatments including water, washing, acid and alkaline perspiration, rubbing, alkalis, and acetic acid cross dyeing. They are fast to dry cleaning and stable to crease resistant finishing and to acid and alkaline hydrolytic influences.

In the following examples the parts and percentages are by weight and the temperatures are given in degrees centigrades.

EXAMPLE 1 A solution of 18.4 parts of cyanuric chloride in 70 parts of acetone is prepared at 3035 and added with good stirring to 300 parts of ice-water to form a suspension. A neutral solution of 106.6 parts of copperphthalocyanine-3-sulphonic acid- (3""4'"'-sulphophenylamide)-3,3",3"'-trisulphonic acid in 800 parts of water is run slowly into the suspension at 0.5". The pH of the reaction mixture is maintained between 5 and 6 by the gradual addition of sodium carbonate solution. As soon as no further sodium carbonate solution is consumed, a neutral solution of 106.6 parts of copper phthalocyanine-4- sulphonic acid-(3""-amino-4''-sulphophenyl amide)-4,4" ,4"'-tn'su1phonic acid in 1,200 parts of water is added. The

temperature is raised slowly to 50 while the pH is kept PRINTING METHOD A mercerized cotton fabric is printed with a paste of the following composition:

30 parts of the dye of Example 1 parts of Urea 395 parts of water 450 parts of 3% sodium algin 10 parts of sodium l-nitrob 15 parts of sodium carbonate 1,000 pans ate thickening enzene-3-sulphonate total:

The printed fabric is dried, steamed for 10 minutes at lO2-10 4, rinsed with cold and warm water, soaped at the boil, rinsed again and dried. A turquoise print of good light and wet fastness is obtained.

EXAMPLE 2 18.4 parts of cyanuric chloride are dissolved in 70 parts of acetone at 3035 and the solution is added with vigorous stirring to 300 parts of ice-water to give a suspension. To this is added slowly at 0-5 a neutral solution of 197.2 parts of copper phthalocyanine-S-sulphonic acid-(3"-amino-phenylamide)-3',3",3"'trisulphonic acid in 1,500 parts of water. The pH value is maintained at 5-6 by controlled addition of sodium carbonate solution. As soon as the rate of reaction decreases, the temperature is raised to 50 and the pH adjusted to 7.0-7.5 so that the reaction proceeds to the endpoint. Sodium chloride is added for complete precipitation of the dye, which is then filtered ofi and dried at 7080 with vacuum. The reactive .dye obtained is again of turquoise blue hue and, in view of its excellent build-up properties, it is very suitable for exhaustion dyeing.

Shade of dyeing n celluloslr: A: Hal fibres DYEING METHOD A dyebath is prepared by dissolving 2 parts of the dye of Example 2 in 4,000 parts of softened water at 100 parts of 21 Mel x 11 m X1 Y1 Ex. No.

Do Bluegreen. Reddlsh blue. Turquoise Do. Greenlsh HHHHHHHHCCHHHH H HHHHHHHQHHHHHH mmmmmmmmmmmmmmm mwwww hmmwmwwwwwm M m HHHHHnHHcmowHHH M m HHHHHHHCHHHCHHH H m m; w" u m m h u C n HH m m H m m m m m m n n c m m turquoise.

HHHHHHGHHHHcHHHHoHHHHHHHnnuuuuunHH H HHHHHHCHHHH HHHH HHHHHHHHHHHHHHHHH mHHHHH uu uuuuu uuu u i uul uu u uu ccNNNcccccmNcccNcmNNccuNNcnuNoccoc U mwwmmmwmwmmmwwmwmwmwwmwwmwmmm Y m M HHHHHHCHHHHHHHHHHHHHHHHHHHHHHHHHHH N HHHHHHCHHHHHHHHHHHHHHHHHHHHHHHHHHH uuuu CCC 2 2 H is A m 0 0 ll 0 I A H m MC H wmmv M w w 0 n H H ig m N N mm H s1 m 1 S C 2 C I ew w N t0 6 w 0 w u a f 055g mmw ms n aa sa hcd 606. 6 bd w m tama m f t C der l wm m mm m m PO .1 Mad 0 mm m a M.s

n d h e C an m g n 2 A.

e mm m .m a .m e m a R N N 1 M a h mc e O ent e X 1 z m m a m w m m a m mm A N A cnm m r ae N 1 .mwm mmmhmmm M M. m 0

edmfi mil c S (S S m Cfd.ld he m m d O MW om m r m wmt M .m m .Pmw

O me-n f .m.msmmf m WCe om e m PP .m

{ICU own if mm d b w mom hmo mum 450 11) SU:-N

which can be produced in accordance with the present inven- Hogs- Examples are as follows:

Example 1:

SUz-NH- SOgH Example 2:

n N w 0 b P u C w 3' (28) CHr-CHr-O-CHz-C Hr- G O O 0 Having thus disclosed the invention, what we claim is:

l. A water-soluble phthalocyanine compoundofthe fonnu- C--Halogen wherein each of (PC) and (PC) is, independently, a SO H groups, each phthalocyanine radical being that of a member selected from the group consisting of nonmetallized phthalocyanine, copper phthalocyanine (CuPe) and nickel phthalocyanine;

each of A and A is, independentlv, a divalent bridgimember selected from the group consisting of 5 (m-011F011, kHz-41H v our-( m (,n /(;ii 011 -011:

Oily-CH:

CHz-CH -CH=CHO -cilr-um-o-cm-um I i s o n SOIH 1 each of R R R and R is, independently, hydrogen,

benzyl, lower alkyl, monohydroxy (lower) alkyl, monolower alkoxy (lower) alkyl and mono halo (lower) alkyl; P C S each of X and Y is, independently, a member selected from the group consisting of hydrogen, lower alkyl and hydrox- (s 0,-N y (lower) alkyl; Y2 H the phthalocyanine nuclei being substituted only in the 3- and/or 4- positions; and entire compound containing from 40 wherein each of and is, independently, a radical four to 12 water-solubihzmg groups selected from the group of coppebcomaihing phthalocyanine or that of nickel consisting of sulphonic acid, carboxylic acid and -SO,N(X- comaining phthalocyanine.

2. A water-soluble phthalocyanine compound according to 3 2: 1? is:i & fg; li;zi $f hydrogen clam Ofthe formula Hal is chloroor bromo;

(S can) each of m, n, p and r is a whole number from 1 to 3, inclu- XI 7 sive; n m being equal to 3 or 4, and p+ r being-equal to 3 or ,l .7 has ,7 7." is .l PC' -Sm-N 3. A water-soluble phthalocyamne compound according to S OPNHFAPN EH claim 2 wherein each of PC" and PC'" is a radical of coppercontaining phthalocyanine and Hal is chloro.

N V V.

' Hal 4. A water-soluble phthalocyanine compound according to FN claim 2 in which at least'oneof the bridge members, A and EPFPT TAT gnse fis n miss OCH;

'11 mugs mag and at least one of PC" and PC' is a radical of nickel-containin hthaloc anine.

g p y a, 3', 3,3"'-CuPc\(80r-NH;)= 5

N 5. Thef phthalocyanme compound, according to \m claim 2 o the formula T (50,11 /s0,-r-m NH 3 11 ur 3 3',3",3"-CuPs;(SO;-Nllz); 0m

so,xn-C -so=n so,

5 wherein CuPc is copper phthalocyanine.

; N 9. The phthalocyanine compound according to claim 2 of the formula 1; s0,n 2 v 3, a, 3,"3"-CuPcS0z-NH: /SO2NH SO3H 4,4,4,4-CuPc SOT-NH -21 (503B m wherein CuPc is copper phthalocyanine. \N

SOz-NH- N11 6. The phthalocyanine compound according to rclaim 2 of the formula 40 (80:11): 0 P h m1 wherein u e i." cr r t ocvanine. w I

S02-NH NH 10. The phthalocyanine compound according to l N claim 2 of the formula .4 -Cl (80311):

-s0m a, 3', 3,3'-CuPc SO -NH NH S0|NH -2-;H 3,3,3",3-CuPc I N (smHa 1 wherein CuPc is copper phthalocyanine. N

SOz-NH- NH I II I 7 The phthalocyanine compound accordin t 4'4'4 '4 -CuPc\ g 0 claim 2 of the formula (soak wherein CuPc i.-: copper phthalocyanine. 3, 3',3",3"'-CuPc -s0; --NH2 11. The phthalocyanine compound according to claim 2 of the formula SOT-NH on; N /s0,H

N 41 4, 4', 4,4"-CuPc-(SOzNH2)z 1- SOPNH -:-':H SOFNH f N 3,3,3,3"-CuPc\S02-NH2 SO:H l

v SO;NH NH wherein CuPc is copper phthalocyanine.

4, 4, 4,4"'-CuPc(B0zNH2)z s (H 8. The phthalocyanine compound according to claim 2 of the formula wherein CuPc is copper phthalocyanine.

t i i 733 lOlO43 7 *z gj g UMTED srnrrs PATENT owner fiER'HFlEATE @F QQRREQ'HQN Patent Noa 3,674,783 Dated July 4, 1972 rnvenm g HANS VON TOBEL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Covering page, first column, beneath line 6, "[21] Appl. No. 833,732" insert -[30] Foreign Application Priority Data July 3rd, 1968 Switzerland. 9920/68-. Column 1, line 42, after the formula, "(II)" should read (II) line 47, after the formula, (111)" should read (III) line 73, "compound" should read ssmpound Column 2, line 2, after the formula, (IV)" should read (IV) line 10, "group-1W should read group NH line 25, "represent" should read --=-represent,-; line 50, in each of the formulae, "0" should read line 67, after the formula, insert a semicolon line 75, in the seond formula, "CH -CH should read -CH -(IJH-. Column 3, line 10, after the formula, insert a period line 15, in the second II II formula, should read line 20, in the second formula,

" should read line 23, after each of the formulae, insert a comma in the second formula, "NH-Q" should read NHQ- line 28, in the formula, "-0" should read O-,-; line 30,

in the formula, "-0" should read -C line 35, after each formula, insert a comma in the first formula, O-MNQ" should read =NQ- in the second formula, n afi read "iii-5 (continued) 3 page 2 3 3 TED STATES PATENT ormtr @THFCATE 9F EQ'HQN Patent No. 3,674,783" 7 I Dated July 4, 1972 Inventor-(g9 Hans Von Tobel It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

u line 37, in the formula, E0 Should read line 45, in

first formula, OCH should read OCH in the second Q formula, should read line 50, in the formula,

"NO" should read N--,--; line 55, in the formula, "N 1. I 3

should read -NO,; line 60, in the formula, "NO" should read --=-N-G,-; line 65, after the formula, insert a comma Column 4,

line 4, in the formula, "0" should read 0"."3 line 37, after the formula, insert a comma Column 5, line 44, "fibers" should read =-=-fibers,; line 50, after the formula, insert a comma line 57, after the formula, insert a comma Column 6, line 22, "(3""4""" should read '=-(3""-amino4""- line 28, "4" should read --4",; line 29, ,4'" should read -4""-; line 47, "algin ate" should read alginate-; line 48, "nitrob enzene" should read *-nitrobenzene; line 53, "l02-l0" should read l0 2lO4,--; line 54, delete "4,"; line 66, "3""trisulphonic" should read --3"' -trisulphonic--. Column 9, line 37, in the first formula,

" O should read Column 10, line 25, "Formula" should (continued) page 3 mg UNETED STATES PATENT orrrsr QER'HFMATE @f QWRREMWN Patent no. 3,674,783 Dated July 4, 1972 lnvento -(g) VON TOBEL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

read Formulaeline 33, in the formula, "-NH" should read -NH--; mg

line 44, in the formula, 0 I should read Claim 1,

line 14, iu the S n formula, "-01-! should read -H-,--; line 15, in

CH CH the third formula, '0" should read Q line 16, in the second formula, "OSb Hl' "should read QSO H; in the third formula, "GCH should read Q Q O-01 should read -QC1 in the secohd formula, "0-" CH line 17, in the first formula,

COOH

should read in the third formula, "0 COOH" should read coon 3 COOH; line 18, in the second formula, 3 G should read llne 19, 111 the flrst formula, 3 (contlnued) Page 4 22;;3 he STATES PATENT were CE TEICATE @F l EQTKQN Patent No, ,7 v Dated July 4, 1972 InventorQ) HANS VON TOBEL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

S0 H SO H a 3 3 a should read in the second formula, "CH" should read CH" should read -CH -CH--;

- in the third formula =-CH-,-=; line 20, {in the first formula, "CH

in the second formula, "CH should read -CH should read -cH -,=g line 21., after the formula, insert a comma line 22, in the first formula, "-0," should read SO H SO H in the second formula, "0CH CH should read --O-CH -CH line 23, in

the first formula, 6," should read O after the second formula insert a comma line 24, in the second formula, "NH-O" should read -NHC line 25, after the formula, insert a comma line 26,

in the formula, "N-O should read --NO,=--; line 27 after the formula,

insert a comma line 28, after the second formula, insert a comma N" should read O-N; OH

should read OH after the second formula, insert a comma line 29, in the second formula,

(continued) page 5 laltent No, 3,674,783 Dated July 4, 1972 Inventorw) HANS VON TOBEL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

line 30, in the second formula, "N should read -N line 31, after the second formula, insert a comma line 32, after the second formula, insert a comma line 33, in the formula, "0

should read ON=N- after the formula, insert a comma line 34, in the formula, "N=N- should read -N=N- line 35,

after the formula, insert a semicolon, Claim 2, line 3, in the formula,

"S0 -NH-A NH" should read -T0 NH-A -NH-; line 3, delete the formula,

I"- PC (SO H)P /X2 (SO2N\Y 2 1 "PC"'(SO H)p". Claim line 4, after the third formula, insert a comma l X 2 (s0 -1\x Y 2 r-l I y; line 5, in the second formula, "HO S" should read --HO S-; line 6,

in the second formula, 'Y should read in the third L(continued) page 0 ems PATENT erwtr cErHeArE r eere'rw Pateht N0. 3,674,783 Dated July 4, 1972 lnventora) HANS vo TOBEL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

W, HO gr W formula N' should read N- after the third formula,

N i N insert a comma line 7, in the first formula, HO should read N v Q ED-; in the second formula,

N HO I N-O-CH=CHO-" should read I I l N SO H SO H 3 3 HO HO N CH=CH NO N=N Q' so H so H CH3 I CH line 8, in the first formula, HO should read HO v CH3 CH3 "80 H" should read -SO H-; in the second formula H0 should read Em (continued) I Page 7 TE STATES PATENT @FFKQE I (5/69) f y I '1 5 I I mwmwn oncmw Patent No, 36749783 Dated y 1972 1nventor( HANS VON TOBEL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby oorreeted as shown below:

$73111: 1 U HO "CH should read "GHQ W SO H SO H Signed and. sealed this 5th day of February'l974.

(SEAL) Attest: v

EDWARD M.FLETCHER,JR. RENE D. TEGTMEYER Attesting Officer Acting Commissioner of Patents 

2. A water-soluble phthalocyanine compound according to claim 1 of the formula
 3. A water-soluble phthalocyanine compound according to claim 2 wherein each of PC'''' and PC'''''' is a radical of copper-containing phthalocyanine and Hal is chloro.
 4. A water-soluble phthalocyanine compound according to claim 2 in which at least one of the bridge members, A1 and A2, is of one of the formulae 